U.S. patent application number 17/631980 was filed with the patent office on 2022-08-25 for biocidal dispersions for coating compositions.
The applicant listed for this patent is Corning Incorporated. Invention is credited to Bavani Balakrisnan, David Michael Fasano, Bryan Patrick Livengood, Joseph Martin Rokowski.
Application Number | 20220264889 17/631980 |
Document ID | / |
Family ID | 1000006375610 |
Filed Date | 2022-08-25 |
United States Patent
Application |
20220264889 |
Kind Code |
A1 |
Balakrisnan; Bavani ; et
al. |
August 25, 2022 |
BIOCIDAL DISPERSIONS FOR COATING COMPOSITIONS
Abstract
According to various examples of the present disclosure, a
biocidal dispersion includes one or more inorganic glass comprising
copper particles. The biocidal dispersion further includes a
dispersant, a thickener, or a mixture thereof. The inorganic glass
comprising copper is homogenously distributed about the biocidal
dispersion and is in a range of from about 3 wt % to about 88 wt %
of the biocidal dispersion.
Inventors: |
Balakrisnan; Bavani;
(Corning, NY) ; Fasano; David Michael; (Lansdale,
PA) ; Livengood; Bryan Patrick; (Nicholasville,
KY) ; Rokowski; Joseph Martin; (Barto, PA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Corning Incorporated |
Corning |
NY |
US |
|
|
Family ID: |
1000006375610 |
Appl. No.: |
17/631980 |
Filed: |
August 4, 2020 |
PCT Filed: |
August 4, 2020 |
PCT NO: |
PCT/US2020/044835 |
371 Date: |
February 1, 2022 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
62883788 |
Aug 7, 2019 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A01P 1/00 20210801; A01N
59/20 20130101; A01N 25/04 20130101; A01N 25/24 20130101 |
International
Class: |
A01N 59/20 20060101
A01N059/20; A01N 25/04 20060101 A01N025/04; A01N 25/24 20060101
A01N025/24; A01P 1/00 20060101 A01P001/00 |
Claims
1. A biocidal dispersion comprising: one or more copper particles
components homogenously distributed about the biocidal dispersion;
and a dispersant, a thickener, or a mixture thereof, wherein the
copper particles components comprise from about 3 wt % to about 88
wt % of the biocidal dispersion.
2. The biocidal dispersion of claim 1, wherein the one or more
copper particles components comprise one or more inorganic glass
comprising copper particles.
3. The biocidal dispersion of claim 2, wherein the one or more
inorganic glass comprising copper particles comprise from about 20
wt % to about 65 wt % of the biocidal dispersion.
4. The biocidal dispersion of claim 2, wherein a median size of the
one or more inorganic glass comprising copper particles is in a
range of from about 1 .mu.m to about 15 .mu.m.
5. The biocidal dispersion of claim 2, wherein the one or more
inorganic glass comprising copper particles independently comprise
an inorganic glass comprising SiO.sub.2, Al.sub.2O.sub.3, CaO, MgO,
P.sub.2O.sub.5, B.sub.2O.sub.3, K.sub.2O, ZnO, Fe.sub.2O.sub.3, or
a mixture thereof.
6. The biocidal dispersion of claim 1, wherein the dispersant, the
thickener, or mixture thereof, comprises an organic solution or an
aqueous solution.
7. The biocidal dispersion of claim 1, wherein the dispersant, the
thickener, or mixture thereof, comprises cellulose, an acrylic acid
containing polymer, a urethane, or a mixture thereof.
8. The biocidal dispersion of claim 1, comprising the thickener,
wherein the thickener comprises hydroxyethyl cellulose, methyl
cellulose, carboxymethyl cellulose, or a mixture thereof.
9. The biocidal dispersion of claim 1, further comprising a pH
modifier, wherein a pKa of the pH modifier is in a range of from
about 4.7 to about 14.
10. (canceled)
11. A coating composition comprising: the biocidal dispersion of
claim 1; one or more emulsion polymers; a second pH modifier; and a
second organic solvent or a second aqueous solvent.
12. The coating composition of claim 11, wherein the one or more
emulsion polymers have a weight-average molecular weight of at
least 15,000 Daltons.
13. The coating composition of claim 11, wherein a viscosity of the
coating composition is in a range of from about 70 KU to about 130
KU.
14. The coating composition of claim 11, wherein a pH of the
coating composition is in a range of from about 6 to about 9.5.
15. The coating composition of claim 11, wherein the coating
composition is configured to kill a microbe chosen from a bacteria,
a virus, a fungi, or a mixture thereof.
16. The coating composition of claim 11, wherein a log reduction of
the coating composition is at least about 2.
17. The coating composition of claim 11, wherein a CIEL*a*b* delta
E* of the coating composition is less than about 15.
18. A method of making the biocidal dispersion of claim 1, the
method comprising: combining the one or more copper particles
components and the dispersant, thickener, or a mixture thereof, to
form a dispersion precursor; and mixing the dispersion precursor to
form the biocidal dispersion.
19. A method of making a coating composition, the method
comprising: combining the biocidal dispersion of claim 1, with one
or more emulsion polymers, a second pH modifier, and a second
organic solvent or a second aqueous solvent to form a coating
composition precursor; and mixing the coating composition precursor
in an aqueous medium to form the coating composition.
20. A dried product of the coating composition of claim 11.
21. The dried product of claim 20, further comprising a secondary
coat at least partially covering the dried product, wherein the
secondary coat is substantially porous to allow copper released
from the copper particles components to be released through the
secondary coat to an external environment.
22. (canceled)
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of priority under 35
U.S.C. .sctn. 119 of U.S. Provisional Application No. 62/883,788
filed Aug. 7, 2019, the content of which is incorporated herein by
reference in its entirety.
BACKGROUND
[0002] Coatings or compositions such as paint can be applied on a
substrate or surface or stored in a container. Over time, the
coating or composition can be exposed to a number of undesired
contaminants such as bacteria, viruses, mildew, mold, fungi, algae
and the like. Exposure to these contaminants can render the coating
or composition visually unattractive or unsuitable for a particular
purpose or present a health hazard. It can therefore be desirable
to mitigate the ability of the undesired contaminants to thrive
once in contact with a coating or composition.
SUMMARY OF THE DISCLOSURE
[0003] According to various examples of the present disclosure, a
biocidal dispersion includes one or more inorganic glass comprising
copper particles. The biocidal dispersion further includes a
dispersant, thickener, or a mixture thereof. The inorganic glass
comprising copper is homogenously distributed about the biocidal
dispersion and is in a range of from about 3 wt % to about 88 wt %
of the biocidal dispersion.
[0004] According to various examples of the present disclosure, a
coating composition includes a biocidal dispersion. The biocidal
dispersion includes one or more inorganic glass comprising copper
particles. The biocidal dispersion further includes a dispersant,
thickener, or a mixture thereof. The inorganic glass comprising
copper is homogenously distributed about the biocidal dispersion
and is in a range of from about 3 wt % to about 88 wt % of the
biocidal dispersion. The coating further includes one or more
emulsion polymers, a pH modifier, and an organic or aqueous
solvent.
[0005] According to various examples of the present disclosure, a
method of making a biocidal dispersion is described. The biocidal
dispersion includes one or more inorganic glass comprising copper
particles. The biocidal dispersion further includes a dispersant,
thickener, or a mixture thereof. The inorganic glass comprising
copper is homogenously distributed about the biocidal dispersion
and is in a range of from about 3 wt % to about 88 wt % of the
biocidal dispersion. The method includes combining one or more
inorganic glass comprising copper particles and dispersant,
thickener, or a mixture thereof to form a dispersion precursor. The
method further includes mixing the dispersion precursor to form the
biocidal dispersion.
[0006] According to various examples of the present disclosure, a
method of making a coating composition is described. The coating
composition includes a biocidal dispersion. The biocidal dispersion
includes one or more inorganic glass comprising copper particles.
The biocidal dispersion further includes a dispersant, thickener,
or a mixture thereof. The inorganic glass comprising copper is
homogenously distributed about the biocidal dispersion and is in a
range of from about 3 wt % to about 88 wt % of the biocidal
dispersion. The coating composition further includes one or more
emulsion polymers, a pH modifier, and an organic or aqueous
solvent. The method includes combining the biocidal dispersion with
one or more emulsion polymers, a pH modifier, and an organic
solvent or aqueous solvent.
[0007] According to various examples of the present disclosure, a
dried product is described. The dried product is a dried product of
a coating composition. The coating composition includes a biocidal
dispersion. The biocidal dispersion includes one or more inorganic
glass comprising copper particles. The biocidal dispersion further
includes a dispersant, thickener, or a mixture thereof. The
inorganic glass comprising copper is homogenously distributed about
the biocidal dispersion and is in a range of from about 3 wt % to
about 88 wt % of the biocidal dispersion. The coating composition
further includes one or more emulsion polymers, a pH modifier, and
an organic or aqueous solvent.
[0008] According to various examples of the present disclosure an
assembly includes a substrate and a coating composition distributed
on the substrate. The coating composition includes a biocidal
dispersion. The biocidal dispersion includes one or more inorganic
glass comprising copper particles. The biocidal dispersion further
includes a dispersant, thickener, or a mixture thereof. The
inorganic glass comprising copper is homogenously distributed about
the biocidal dispersion and is in a range of from about 3 wt % to
about 88 wt % of the biocidal dispersion. The coating composition
further includes one or more emulsion polymers, a pH modifier, and
an organic or aqueous solvent.
[0009] According to various examples of the present disclosure a
method of making an assembly includes applying a coating
composition to at least a portion of a substrate. The coating
composition includes a biocidal dispersion. The biocidal dispersion
includes one or more inorganic glass comprising copper particles.
The biocidal dispersion further includes a dispersant, thickener,
or a mixture thereof. The inorganic glass comprising copper is
homogenously distributed about the biocidal dispersion and is in a
range of from about 3 wt % to about 88 wt % of the biocidal
dispersion. The coating composition further includes one or more
emulsion polymers, a pH modifier, and an organic or aqueous
solvent. The method includes combining the biocidal dispersion with
one or more emulsion polymers, a pH modifier, and an organic
solvent or aqueous solvent. The method further includes drying the
composition thereon.
DETAILED DESCRIPTION
[0010] Reference will now be made in detail to certain examples of
the disclosed subject matter. While the disclosed subject matter
will be described in conjunction with the enumerated claims, it
will be understood that the exemplified subject matter is not
intended to limit the claims to the disclosed subject matter.
[0011] Various examples of the present disclosure relate to a
biocidal dispersion. The biocidal dispersion can be used as an
additive that can be incorporated into a coating composition to add
biocidal activity to the coating composition. The biocidal
dispersions described herein can include one or more copper
particles components homogenously distributed in a dispersant,
thickener, or a mixture thereof. For example, the copper particles
components can include inorganic glass comprising copper particles,
copper oxide comprising copper particles, copper metal comprising
copper particles, or combinations thereof. A median size of the one
or more inorganic glass comprising copper particles can be in a
range of from about 1 .mu.m to about 15 .mu.m, about 3 .mu.m to
about 8 .mu.m, about 4 .mu.m to about 6 .mu.m, less than, equal to,
or greater than about 1 .mu.m, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,
13, 14, or about 15 .mu.m. The median size can be determined by
analyzing the major dimension of the individual inorganic glass
comprising copper particles. The major dimension, on an individual
basis, can be a measurement of the diameter, width, or length of
the individual inorganic glass comprising copper particles.
[0012] The copper particles components can be present in a range of
from about 3 wt % to about 88 wt % of the biocidal dispersion,
about 10 wt % to about 87 wt %, about 42 wt % to about 85 wt %,
less than, equal to, or greater than about 3 wt %, 4, 5, 6, 7, 8,
9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25,
26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42,
43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59,
60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76,
77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, or about 88 wt %.
[0013] In embodiments including inorganic glass comprising copper
particles, the inorganic glass portion of the individual inorganic
glass comprising copper particle component can include any suitable
material such as SiO.sub.2, Al.sub.2O.sub.3, CaO, MgO,
P.sub.2O.sub.5, B.sub.2O.sub.3, K.sub.2O, ZnO, Fe.sub.2O.sub.3,
nanoparticles thereof, or a mixture thereof. The copper of the
inorganic glass comprising copper particles can be present in an
individual inorganic glass comprising copper particle in any
suitable amount. For example, the copper can be present in a range
of from about 5 wt % to about 80 wt % of the individual inorganic
glass comprising copper particle, about 10 wt % to about 70 wt %,
about 25 wt % to about 35 wt %, about 40 wt % to about 60 wt %,
about 45 wt % to about 55 wt %, less than, equal to, or greater
than about 5 wt %, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65,
70, 75, or about 80 wt %. In each inorganic glass comprising copper
particle, the copper portion can independently include a Cu metal,
Cu.sup.+, Cu.sup.2+, or a combination of Cu.sup.+ and Cu.sup.2+.
The copper can be non-complexed or can have a ligand bonded thereto
to form a complex. Although the inorganic glass comprising copper
particle is effective as a biocidal agent, a potential drawback is
that the copper offers numerous opportunities for ligands to attach
thereto, resulting in complexes that can alter the color of a
coating composition to which it is ultimately incorporated.
However, it is possible to pair the inorganic glass comprising
copper particles with various additional additives in order to
limit the extent to which the copper is complexed and therefore the
color of the coating composition is altered from a standard.
[0014] For example, in a coating composition to which the biocidal
dispersion is incorporated, it is possible to achieve a CIEL*a*b*
delta E* between the observed color and a standard (e.g., a
dispersion or coating including the same constituents, but are free
of or include a different amount of the glass comprising copper) of
less than about 15, less than about 14, less than about 13, less
than about 12, less than about 11, less than about 10, less than
about 9, less than about 8, less than about 7, less than about 6,
less than about 5, less than about 4, less than about 3, less than
about 2, less than about 1, in a range of from about 1 to about 15,
about 2 to about 13, about 5 to about 10, about 3 to about 8, about
4 to about 7, about 5 to about 6, less than, equal to, or greater
than about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,
17, 18, 19, 20, 21, 22, 23, 24, or about 25. As understood, the
CIEL*a*b* color scale is a scale for determining a color. Using
this test, the difference (e.g., a delta E*) in color between a
standard and observed color can be measured. In this manner, the
extent to which the desired color of a coating is altered by the
components therein can be measured.
[0015] In operation, the copper from the biocidal dispersion can be
released into the coating composition to interact with and kill
unwanted biological contaminants such as microbes in the
composition. Examples of microbes that the copper can kill include
Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas
aeruginosa, Methicillin Resistant, E. coli, Enterobacter cloacae,
Acinetobacter baumannii, Enterococcus faecalis, Klebsiella
pneumoniae, Klebsiella aerogenes, Staphylococcus aureus, and
mixtures thereof. Examples of viruses that the copper can kill
include Influenza H1N1, Adenovirus 5, and Norovirus. An example of
a fungi the copper can kill includes Candida auris. The
effectiveness of the dispersion or coating composition as a
biocidal coating can be measured as a function of the coating
composition's log reduction. The coating composition's log
reduction value can be relevant to its ability to kill biological
organisms to which it is exposed, but can also allow the inorganic
glass comprising copper to act as a preservative for the coating
composition during storage (e.g., in a container such as, but not
limited to a tank, can, bucket, drum, bottle, or tube).
[0016] According to various examples, a log reduction of the
biocidal dispersion, or of the coating to which it is incorporated,
can be at least about 2, at least about 3, at least about 4, at
least about 5, at least about 6, at least about 7, at least about
8, at least about 9, at least about 10, in a range of from about 1
to about 10, about 3 to about 7, about 4 to about 6, or less than,
equal to, or greater than about 1, 2, 3, 4, 5, 6, 7, 8, 9, or about
10. The log reduction value can be measured according to the ASTM
D2574-16 (2016) Standard test method for resistance of emulsion
paints in the container to attack by microorganisms. An example of
an advantage to using the inorganic glass comprising copper
components described herein is that the copper is less corrosive,
and toxic, than many organic biocidal compounds that are included
in corresponding coating compositions.
[0017] In the biocidal dispersion, the individual copper particles
components are dispersed with a dispersant, thickener, or a mixture
thereof, which is at least partially soluble in the carrier liquid.
Suitable dispersants include those that are able to facilitate a
homogenous distribution of the copper components. For example,
suitable dispersants or thickeners can help to mitigate the
possibility of a substantial amount of the copper comprising glass
particles falling out of suspension as a sediment. The ability of
the dispersant or thickener to help prevent sedimentation can be
determined, for example, by a test such as ASTM D5590 or ASTM
D2574. Thus, the biocidal dispersion is considered a stable
dispersion. According to various examples, it can be possible for
the biocidal dispersion or coating composition to which the
dispersion is incorporated to be free of a sediment of the copper
particles components for a time period in a range of from about 1
day to about 365 days, about 5 days to about 90 days, less than
equal to or greater than about 1 day, 5, 10, 15, 20, 25, 30, 35,
40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115,
120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 175, 180, 185,
190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250,
255, 260, 265, 270, 275, 280, 285, 290, 295, 300, 305, 310, 315,
320, 325, 330, 335, 340, 345, 350, 355, 360, or about 365 days.
While not so limited, examples of suitable organic dispersants can
include an acrylic acid containing copolymer, a urethane, a
carboxylate containing oligomer, an amine containing oligomer, a
phosphate containing oligomer, a sulfonate containing oligomer, an
anhydride containing oligomer, or a mixture thereof. Examples of
suitable thickeners that can be used include celluloses. Examples
of celluloses can include hydrophobically modified celluloses. More
specific, though non-limiting, examples of suitable celluloses can
include hydroxyethyl cellulose, methyl cellulose, carboxymethyl
cellulose, or a mixture thereof. In some examples, the dispersant
can include any of the constituents mentioned herein as well as
water. For example, a dispersant can include a carboxylate
containing oligomer, an amine containing oligomer, a phosphate
containing oligomer, a sulfonate containing oligomer, an anhydride
containing oligomer, or a mixture thereof that are dispersed in
water.
[0018] As stated herein the biocidal dispersion can be an
individual component that can be added to a coating composition in
order to effectively deliver the copper particles components.
According to various examples, a non-limiting benefit to adding the
copper particles components, as part of a biocidal dispersion, to a
coating composition is that the distribution of the copper
particles components in the coating composition can be improved
relative to mixing the copper particles components alone into the
coating composition directly. For example, if the coating
composition itself is particularly thick or viscous, direct
addition of the copper particles components can take quite a bit of
effort to mix into coating composition. This can be because the
copper particles components can be added as an aggregate that will
require dispersion into the coating composition. By contrast, if
the copper particles components are effectively pre-dispersed, by
virtue of being a component of the biocidal dispersion, it can be
easier or quicker to disperse the copper particles components in
the coating composition. This can be because the copper comprising
glass particles are already dispersed upon contact with the coating
composition. Additionally, according to some examples, including
the copper particles components as a pre-dispersed mixture can lead
to the copper particles components being dispersed in the coating
composition more quickly.
[0019] In some examples, the biocidal dispersion can include only
the copper particles components and a dispersant, a thickener, or a
mixture thereof. However, in further examples, the biocidal
dispersion can include additional components. These additional
components can be components chosen to convey certain desirable
properties to the biocidal dispersion. In some examples, the
additional components added to the biocidal dispersions can be
components that are also present in a coating composition to which
the biocidal dispersion is mixed. Examples of suitable additional
components can include a cosolvent, a pH modifier, a surfactant, a
defoamer or air release agent, a rheological pigment, a stabilizer,
a rheology modifier, or a mixture thereof. Examples of suitable
cosolvents can include any of the aqueous or organic solvents
described herein and can additionally include isopropanol, xylene,
butyl acetate, or a mixture thereof.
[0020] In some embodiments, the biocidal dispersion is free or
substantially free of resins or binders (e.g., conventional resins
or binders used in paint or coating compositions). For example, the
biocidal dispersion comprises less than 5%, less than 1%, less than
0.5%, or less than 0.1% by weight of the resins or binders.
Examples of such resins or binders may include, without limitation,
one or more of phenolic resin, urea formaldehyde resin, epoxy
resin, unsaturated polyester, polyurethane resin, silicone resin,
alkyd resin, acrylic resin (e.g., acrylic ester), epoxy resin,
polyethylene (PE), polyvinyl chloride (PVC), polystyrene (PS),
polyvinyl acetate (PVAC), polypropylene (PP), polymethacrylic acid
(PMMA), acrylonitrile butadiene styrene (ABS), copolymers thereof,
or combinations thereof.
[0021] A pH modifier can be used to maintain a pH of the biocidal
dispersion to be in a range of from about 6 to about 9.5, about 7.5
to about 9, about 7.5 to about 8.5, less than, equal to, or greater
than about 6, 6.5, 7, 7.5, 8, 8.5, 9, or about 9.5. Maintaining a
pH in this range can be helpful to influence the reactivity of
copper ions with other materials in the biocidal dispersion or in
the coating composition. Ultimately, this can affect the color of
the coating composition as a whole. Moreover, the pH of the
biocidal dispersion or coating composition can impact the shelf
life and viscosity of the biocidal dispersion or coating
composition.
[0022] The pH modifier or modifiers can independently have a pKa in
a range of from about 4.7 to about 14, about 5 to about 9.5, about
6 to about 9.5, about 7 to about 9.5, less than, equal to, or
greater than about 4.7, 4.8, 4.9, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6,
5.7, 5.8, 5.9, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7,
7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8, 8.1, 8.2, 8.3, 8.4,
8.5, 8.6, 8.7, 8.8, 8.9, 9, 9.5, 9.6, 9.7, 9.8, 9.9, 10, 10.1,
10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11, 11.1, 11.2,
11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12, 12.1, 12.2, 12.3,
12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13, 13.1, 13.2, 13.3, 13.4,
13.5, 13.6, 13.7, 13.8, 13.9, or about 14. The pH modifier can be
present in the biocidal dispersion in a range of from about 0.1 wt
% to about 5 wt % of the biocidal dispersion, about 0.5 wt % to
about 2 wt %, about 1 wt % to about 1.5 wt %, less than, equal to,
or greater than about 0.1 wt %, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4,
4.5, or about 5 wt %.
[0023] Specific non-limiting examples of suitable pH modifiers of
buffer solutions include those selected from the group of Group (I)
hydroxides; Group (II) hydroxides; and organic amines. More
specific non-limiting examples of suitable pH modifiers include
those selected from metal hydroxides, ammonium hydroxide, and
amines, wherein the amines are amines of the formula NH.sub.2R,
wherein R is selected from the group consisting of H, OR' or
--R'--OH, wherein R' is selected from the group consisting of --H,
alkane, and alkylene. Specific further non-limiting examples of
suitable pH modifiers include potassium hydroxide, sodium
hydroxide, 2-amino-2-methyl-1-propanol, ammonia,
2-dimethylamino-2-methyl-1-propanol, 2-butylaminoethanol,
N-methylethanolamine, 2-amino-2-methyl-1-propanol,
monoisopropanolamine, monoethanolamine, N,N dimethylethanolamine,
N-butyldiethanolamine, 2-amino-2-ethyl-1,3-propanediol,
2-amino-2-hydroxymethyl-1,3-propanediol, triethanolamine. Specific
further non-limiting examples of suitable pH modifiers include a
mixture of at least one of potassium hydroxide and sodium hydroxide
and at least one of 2-amino-2methyl-1-propanol and ammonia, in
which at least one of potassium hydroxide and sodium hydroxide, or
a mixture thereof are the major component of the pH modifier
mixture. In some examples, it can be desirable to avoid a pH
modifier that includes ammonia or amines. This is because ammonia
and amines can engage in undesirable reactions with the copper and
create undesirable colors in the biocidal dispersion.
[0024] A defoamer or air release agent can be used to help the
biocidal dispersion to avoid forming or stabilizing air bubbles. In
some examples, air bubbles can be damaging because air bubbles can
cause undesirable oxidation of the copper in the wet state. Air
bubbles that are in turn transmitted from the biocidal dispersion
to the coating composition can cause defects in the resulting film
that is ultimately formed from the coating composition. The
defoamer or air release agent can include mineral oil, silicone,
siloxane, phosphate, fatty alcohol, fatty acids or esters,
polyethylene glycol or polyacrylates. According to further
examples, the defoamer air release agent can be free of a silicone.
It can be beneficial for the defoamer or air release agent to be
free of a silicone because silicones may unfavorably alter the
distribution of copper in the inorganic glass comprising copper
component. The defoamer or air release agent can be in a range of
from about 0.5 wt % to about 40 wt % of the biocidal dispersion,
about 1 wt % to about 10 wt %, less than, equal to, or greater than
about 0/5 wt %, 1, 5, 10, 15, 20, 2,5 30, 35, or about 40 wt %.
[0025] The biocidal dispersion can further include a rheological
pigment such as a clay component such as attapulgite, laponite,
bentonite, or a mixture thereof. Other examples of a rheological
pigment can include a fumed silica. The rheological pigment can be
in a range of from about 0.5 wt % to about 40 wt % of the biocidal
dispersion, about 1 wt % to about 10 wt %, less than, equal to, or
greater than about 0.5 wt %, 1, 5, 10, 15, 20, 25, 30, 35, or about
40 wt %. In some examples, the rheological pigment can be part of a
rheology modifier or thickener component in the biocidal
dispersion. Where present, the rheology modifier can be in a range
of from about 0.1 wt % to about 5 wt % of the coating composition,
about 0.5 wt % to about 2 wt %, about 0.7 wt % to about 1.5 wt %,
about 1 wt % to about 1.25 wt %, less than, equal to, or greater
than about 0.1 wt %, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1,
1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4,
2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8,
3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or about 5 wt
%. Examples of suitable rheological modifiers include a thickener
comprising any of the rheological pigments described herein,
hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose,
hydroxyethylcellulose, an alkali swellable emulsion, a
hydrophobically modified ethoxylated urethane, hydrophobically
modified analogues, natural or synthetic gums thereof, or a mixture
thereof.
[0026] As stated herein, the rheology modifier can control a
viscosity of the biocidal dispersion. According to various
examples, the viscosity of the biocidal dispersion can be
controlled to be in a range of from about 70 KU to about 130 KU,
about 75 KU to about 120 KU, about 80 KU to about 115 KU, about 90
KU to about 110 KU, about 95 KU to about 105 KU, less than, equal
to, or greater than about 70 KU, 75, 80, 85, 90, 95, 100, 105, 110,
115, 120, 125, or about 130 KU. The viscosity can be measured using
any suitable instrument such as a Brookfield KU-2 viscometer. Other
rheological properties of the biocidal dispersion that can be
controlled can include the ability for the biocidal dispersion to
be resistant to settling and syneresis during storage.
[0027] The biocidal dispersion can further include a stabilizer.
The stabilizer can include a component such as an organophosphate,
an ammonium phosphate, a potassium tripolyphosphate, or a mixture
thereof. The stabilizer can be in a range of from about 0.5 wt % to
about 20 wt % of the biocidal dispersion, about 2 wt % to about 10
wt %, less than, equal to, or greater than about 0.5 wt %, 1, 2, 3,
4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or about
20 wt %.
[0028] The biocidal dispersion can be easily prepared according to
various methods. For example, any of the components described
herein can be combined into a biocidal dispersion precursor. The
precursor can be mixed for an amount of time to form the biocidal
dispersion. The biocidal dispersion can be mixed at any temperature
including at about room temperature (e.g., 25.degree. C.). After
the biocidal dispersion is prepared, it can be incorporated into a
coating composition.
[0029] Once the biocidal dispersion is incorporated into the
coating composition, the concentration of the copper particles
components (e.g., the glass comprising copper component) can be in
a range of from about 0.01 wt % to about 15 wt % of the coating
composition, about 2 wt % to about 8 wt % about 0.1 wt % to about 2
wt %, about 0.5 wt % to about 1 wt %, less than, equal to, or
greater than about 0.01 wt %, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07,
0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2,
1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4,
4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4, 5.6, 5.8, 6, 6.2, 6.4, 6.6, 6.8,
7, 7.2, 7.4, 7.6, 7.8, 8, 8.2, 8.4, 8.6, 8.8, 9, 9.2, 9.4, 9.6,
9.8, 10, 10.2, 10.4, 10.6, 10.8, 11, 11.2, 11.4, 11.6, 11.8, 12,
12.2, 12.4, 12.6, 12.8, 13, 13.2, 13.4, 13.6, 13.8, 14, 14.2, 14.4,
14.6, 14.8, or about 15 wt %.
[0030] Additional components of the coating composition can include
any of the additional components mentioned herein with respect to
the biocidal dispersion such as the cosolvent, the dispersant, the
thickener, the pH modifier, the surfactant, the defoamer or air
release agent, the rheological pigment, the stabilizer, the
rheology modifier, or mixtures thereof. These additional components
can be present in the coating composition in a concentration range
substantially in-line with those described herein with respect to
the biocidal dispersion. In some examples, the coating composition
can include any one of or mixtures of the additional components
found in the biocidal coating prior to being mixed with the
biocidal dispersion. In these examples, any of the additional
components that are found in coating composition can be considered
a "second" version of the additional component of the biocidal
dispersion. For example, the coating composition can include a
second cosolvent, a second pH modifier, a second surfactant, a
second defoamer or air release agent, a second rheological pigment,
a second stabilizer, a second rheology modifier, or mixtures
thereof. Where present, the second cosolvent, the second pH
modifier, the second surfactant, the second defoamer or air release
agent, the second rheological pigment, the second stabilizer, or
the second rheology modifier can be the same material as their
counterpart in the biocidal dispersion or it can be a different
material.
[0031] The coating composition can include a latex polymer formed
or produced by emulsion polymerization, otherwise referred to as
one or more emulsion polymers. According to various further
examples, polymers can also include those made by a solution
process and then inverted or dispersed into water. Further examples
of polymers can include non-aqueous dispersions. The one or more
emulsion polymers can independently have a redox potential in a
range of from about -200 mV to about 200 mV, about -175 mV to about
175 mV, about -150 mV to about 150 mV, about -125 mV to about 125
mV, about -100 mV to about 100 mV, about -75 mV to about 75 mV,
about -50 mV to about 50 mV, about -40 mV to about 40 mV, about -30
mV to about 30 mV, about -25 mV to about 25 mV, about -20 mV to
about 20 mV, about 15 mV to about 15 mV, about -9 mV to about 9 mV,
about -8 mV to about 8 mV, about -7 mV to about 7 mV, about -6 mV
to about 6 mV, about -5 mV to about 5 mV, about -4 mV to about 4
mV, about -3 mV to about 3 mV, about -2 mV to about 2 mV, about -1
mV to about 1 mV, less than, equal to, or greater than about -200
mV, -190, -185, -180, -175, -170, -165, -160, -155, -150, -145,
-140, -135, -130, -125, -120, -115, -110, -105, -100, -95, -90,
-85, -80, -75, -70, -65, -60, -55, -50, -45, -40, -35, -30, -29,
-28, -27, -26, -25, -24, -23, -22, -21, -20, -19, -18, -17, -16,
-15, -14, -13, -12, -11, -10, -9, -8, -7, -6, -5, -4, -3, -2, -1,
0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18,
19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 35, 40, 45, 50, 55,
60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130,
135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, or
about 200 mV. Controlling the redox potential of the one or more
emulsion polymers can be helpful to enhance the stability of the
copper particles components and to minimize discoloration. In
examples in which the coating composition includes one or more
emulsion polymers, the polymers can independently have a
weight-average molecular weight of at least about 15,000 Daltons,
at least 50,000 Daltons, at least about 100,000 Daltons, at least
about 500,000 Daltons, at least about 1,000,000 Daltons in a range
of from about 25,000 Daltons to about 10,000,000 Daltons, about
60,000 Daltons to about 2,000,000 Daltons, about 100,000 Daltons to
about 1,000,000 Daltons, less than, equal to, or greater than about
15,000 Daltons, 25,000, 50,000, 75,000, 100,000, 125,000, 150,000,
175,000, 200,000, 225,000, 250,000, 275,000, 300,000, 325,000,
350,000, 375,000, 400,000, 425,000, 450,000, 475,000, 500,000,
1,000,000, 2,000,000, 3,000,000, 4,000,000, 5,000,000, 6,000,000,
7,000,000, 8,000,000, 9,000,000, or about 10,000,000 Daltons.
[0032] According to various examples, the emulsion polymers can
include one or more repeating units derived from monomers that can
include a polymerizable phosphorous-containing monomer, an
acetoacetoxy-functional acrylate, an acetoacetoxy-functional
methacrylate, an acetoacetoxy-ethylmethacrylate, or a mixture
thereof. Examples of suitable polymerizable phosphorous monomers
include those having the structure according to Formula I, Formula
II, or a mixture thereof:
##STR00001##
In either of Formula I or Formula II, R.sup.1, R.sup.2, R.sup.3,
R.sup.4, and R.sup.5, can be independently selected from --H, --OH,
and substituted or unsubstituted (C.sub.1-C.sub.20)hydrocarbyl,
which can independently include at least one unsaturated
polymerizable group. In further examples, R.sup.1, R.sup.2,
R.sup.3, R.sup.4, and R.sup.5, are independently selected from --H,
--OH, substituted or unsubstituted (C.sub.1-C.sub.20)alkyl,
substituted or unsubstituted (C.sub.1-C.sub.20)alkenyl, substituted
or unsubstituted (C.sub.1-C.sub.20)alkynyl, substituted or
unsubstituted (C.sub.1-C.sub.20)alkoxy, substituted or
unsubstituted (C.sub.1-C.sub.20)acyl, substituted or unsubstituted
(C.sub.1-C.sub.20)cycloalkyl, substituted or unsubstituted
(C.sub.1-C.sub.20)aryl, and mixtures thereof. Specific examples of
polymerizable phosphorous-containing monomers can include a vinyl
phosphonic acid monomer, an allyl phosphonic acid monomer, a
2-acrylamido-2-methylpropanephosphonic acid monomer, an
.alpha.-phosphonostyrene monomer, a
2-methylacrylamido-2-methylpropanephosphonic acid monomer, a
1,2-ethylenically unsaturated (hydroxy)phosphinylalkyl
(meth)acrylate monomer, a (hydroxy)phosphinylmethyl methacrylate, a
dihydrogen phosphate monomer (e.g., monomers chosen from
2-phosphoethyl (meth)acrylate, 2-phosphopropyl (meth)acrylate,
3-phosphopropyl (meth)acrylate, and 3-phospho-2-hydroxypropyl
(meth)acrylate), or mixtures thereof.
[0033] Acetoacetoxy-ethylmethacrylate monomers can be repeating
units in an emulsion polymer. Phosphate acrylate monomer and
acetoacetoxy-ethylmethacrylate can be a useful monomer in a polymer
composition because it can scavenge copper ions and can further
react with the copper ions to create a slow controlled release of
copper ions from the inorganic glass comprising copper component.
Moreover, the capture of copper by Acetoacetoxy-ethylmethacrylate
can help to reduce color generation because of the pendant nature
of Acetoacetoxy-ethylmethacrylate structure, which makes the copper
releasable under certain conditions.
[0034] The coating composition can include a variety of initiators.
The initiators can be water soluble and can include, for example,
sodium persulfate (Na.sub.2S.sub.2O.sub.8) and potassium persulfate
(K.sub.2S.sub.2O.sub.8); peroxides such as hydrogen peroxide and
tert-butyl hydroperoxide (t-BHP); and azo compounds such as those
available under the trade designation VAZO.TM. initiators,
available from the Chemours Company, Wilmington, Del. The coating
composition can further include an activator such as a bisulfite, a
metabisulfite, ascorbic acid, erythorbic acid, sodium formaldehyde
sulfoxylate, ferrous sulfate, ferrous ammonium sulfate, and ferric
ethylenediamine tetraacetic acid.
[0035] According to some examples, the coating compositions
described herein can be free of a chelator. The chelator can
function to bind components of the coating composition, which can
help to keep the components in solution or to prevent certain
components from participating in undesired reactions. However, the
chelator can also bind or complex with the copper thus rendering
the copper unsuitable as a biocide. If a chelator is included, it
can be important to carefully select certain chelators that either
will not complex with the copper of the copper particles components
or will not react to such an extent that the copper cannot function
as a biocidal agent. An example of a suitable chelator that can be
used or not, depending on the particular application, is
ethylenediaminetetraacetic acid (EDTA).
[0036] According to various examples, the coating composition can
include one or more pigments, which can include a pigment, a
colorant or an extender. The colorants can give the coating
composition its color, when for example, the coating composition is
a paint composition. Where present, any of the pigment, extender,
or the colorant can independently be in a range of from about 0.1
wt % to about 30 wt % of the coating composition, about 0.2 wt % to
about 10 wt %, about 0.5 wt % to about 7 wt %, about 0.6 wt % to
about 5 wt %, about 0.7 wt % to about 1 wt %, less than, equal to,
or greater than about 0.1 wt %, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8,
0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8,
8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15,
15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20, 20.5, 21, 21.5,
22, 22.5, 23, 23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28,
28.5, 29, 29.5, or 30 wt %. There are many suitable pigments,
colorants, or extenders that can be included in the coating
composition. For example, suitable extenders include rheological
pigments, talc, aluminum trihydrate, barium sulfate, nepheline
syenite, CaCO.sub.3, silica, a flattening agent, zinc oxide, or a
mixture thereof. An example of a pigment can include TiO.sub.2.
According to some examples, it can be desirable for the coating
composition to be free of a colorant that includes manganese
because manganese can react with copper and thus render copper
unsatisfactory as a biocidal agent. According to various examples,
the rheological pigments can serve as a pigment that can
additionally promote additional desired properties in the coating
composition. For example, rheological pigments include clays such
as Attapulgite, a grade of clay, can be used as a rheological
modifier that is capable of increasing viscosity of the coating
composition. According to some examples, the clay can include
hydrous aluminum phyllosilicate and in some examples iron,
magnesium, alkali metals, alkaline earth metals, or mixtures
thereof.
[0037] The coating compositions described herein can be formed
according to any suitable method. For example, the coating
compositions described herein can be formed by combining any
combination or sub-combination of the components described herein,
along with the biocidal dispersion, to form a coating composition
precursor. The coating composition precursor can then be mixed at a
low or high shear in an aqueous medium to form the coating
composition. In further examples, all of the components of the
coating composition, aside from the biocidal dispersion, can be
present as a powder mixture. The powder mixture can be mixed and
then water or an organic solvent can be added to disperse the
components and form a liquid coating composition.
[0038] The coating composition can be dried to form a dried
product. The dried product can be a film or layer having any
desired thickness. Drying can be accomplished by simply exposing
the coating composition to ambient conditions. In some examples, it
can be desirable to expose the dried or even a semi-dried product
to a secondary post-curing procedure. According to various
examples, drying or a secondary post-curing procedure, can be
accomplished, or aided, by exposing the coating composition to
heat, reduced humidity or increased air flow or solar
radiation.
[0039] In the final dried product, it can be desirable to have the
inorganic glass comprising copper component heterogeneously
distributed about the dried product. For example, it can be
desirable to have a major portion of the inorganic glass comprising
copper component located proximate to a surface of the dried
product. For example, in a dried product, over 50 wt % of the
copper particles components can be found between a plane defined by
a surface of the dried product and a substantially parallel plane
extending through the center of the dried product. For example,
about 50 wt % to about 100 wt % of the copper particles components
can be located proximate to the surface of the dried product, or
about 55 wt % to about 95 wt %, about 60 wt % to about 90 wt %,
about 65 wt % to about 85 wt %, about 70 wt % to about 80 wt %,
less than, equal to, or greater than about 55 wt %, 60, 65, 70, 75,
80, 85, 90, 95, or about 100 wt %. Locating the major portion of
the copper particles components proximate to the surface of the
dried product can be desirable to increase the access of the copper
to any microbes to which the dried product is exposed.
[0040] According to some examples, the dried product can further
include a secondary coat of material substantially covering the
dried product. The coat can be a secondary coat of a sealant
material or a bottom primer coat. According to some examples, the
coat covering the dried product can be substantially porous to
allow copper released from the copper particles components to be
released through the coat to an external environment. In further
examples, the dried product can be a top coat that is applied over
a surface or another product. In some examples, where the dried
product is a top coat, the coating composition can be spray coated,
brushed, roller coated, curtain coated, or a combination thereof,
to the surface of the product to which it is coated.
[0041] The coating composition forming the dried product can be
applied to a substrate. For example, if the coating composition is
a paint, the coating composition can be applied to a substrate
including wood, a plastic, a metal, a ceramic, a stone, cement,
drywall. In some examples, a primer material can be applied to the
substrate and the coating composition can be applied thereon. In
some examples, the coating composition can be applied to a
previously coated or weathered surface.
WORKING EXAMPLES
[0042] Various examples of the present disclosure can be better
understood by reference to the following Examples which are offered
by way of illustration. The present disclosure is not limited to
the Examples given herein.
Working Example 1: Stability of Biocidal Dispersions Including
Glass Comprising Copper and a Hydrophobically Modified
Cellulose
[0043] The stability of a biocidal dispersion including a glass
comprising copper available under the trade designation
Guardiant.TM., available from Corning Incorporated, Corning, N.Y.
and a hydrophobically modified cellulose available under the trade
designation Natrosol plus 330 PA.TM., available from Ashland
Specialty Chemical Company, Covington, Ky. was studied by varying
the weight percentages of each component. Results are shown in
Table 1, below. In Table 1, "Y" indicates a stable suspension
(e.g., no sedimentation), "N" indicates an unstable suspension
(e.g., sedimentation present), and "N/A" indicates that the mixture
was not tested.
TABLE-US-00001 TABLE 1 Stability of compositions including Natrosol
plus 330 PA .TM. and Guardiant .TM. Guardiant .TM. wt % Natrosol
plus 330 PA .TM. wt % Stable? 10 0.3 N 10 1 Y 10 1.5 Y 10 3 N 15
0.3 N 15 1 Y 15 1.5 Y 17.5 1 Y 17.5 1.5 Y 20 0.3 N 20 0.75 N 20 1 Y
20 1.25 N 20 1.5 N 20 3 N 40 0.3 N 40 0.75 N 40 1 N 40 1.25 N 40
1.5 N
Working Example 2: Determining the Minimum Bactericidal
Concentration of Compositions Including Natrosol Plus 330 PA.TM.
and Guardiant.TM.
[0044] To determine the minimum bactericidal concentration of the
biocidal dispersions, 1 g of compositions including Guardiant.TM.
were obtained. Sample 1 included 10 wt % Guardiant.TM. and
deionized water, Sample 2 included 10 wt % Guardiant.TM. and 1.5 wt
% Natrosol plus 330 PA.TM.. Sample 3 included 10 wt % Guardiant.TM.
and 1 wt % Natrosol plus 330 PA.TM. (diluted to 50%). Sample 4
included 10 wt % Guardiant.TM. and 1 wt % Natrosol plus 330 PA.TM..
Sample 5 was free of Guardiant.TM. but included 1.5 wt % Natrosol
plus 330 PA.TM..
[0045] For each 1 g sample, 10 microcentrifuge tubes were prepared
along with an additional blank tube. 900 .mu.L of a Tryptic Soy
broth was added to each tube (except the blank, which had 1000
.mu.L of a broth). One of the 10 microcentrifuge tubes was vortexed
and 100 .mu.L of broth was removed and added to the second tube.
This was repeated for the remaining microcentrifuge tubes (except
for the blank) to make serial dilutions. 50 .mu.L of Pseudomonas
aeruginosa was added to each microcentrifuge tube (including the
blank). The microcentrifuge tubes were incubated for 24 hours at
37.degree. C. after which time 100 .mu.L of each tube's contents
were removed and plated. The plates were incubated for 24 hours at
37.degree. C. after which time the plate were observed for
colonies. The results are shown in Table 2. In Table 2, "-"
indicates no bacterial recovery, "+" indicates trace contamination
(<10 colonies), "++" indicates light contamination (<100
colonies), and "+++" indicates heavy contamination (continuous
smear or growth).
TABLE-US-00002 TABLE 2 Minimal Bactericidal Concentration of
compositions including Natrosol plus 330 PA .TM. and Guardiant .TM.
Sample Sample Sample Sample Sample Tube Dilution 1 2 3 4 5 1
1000000 - - - - +++ 2 10000 ++ - +++ - +++ 3 1000 +++ +++ +++ ++
+++ 4 100 +++ +++ +++ +++ +++ 5 10 +++ +++ +++ +++ +++ 6 1 +++ +++
+++ +++ +++ 7 0.1 +++ +++ +++ +++ +++ 8 0.01 +++ +++ +++ +++ +++ 9
0.001 +++ +++ +++ +++ +++ 10 0.0001 +++ +++ +++ +++ +++ 11 Blank
+++ +++ +++ +++ +++
Working Example 3: Stability of Biocidal Dispersions Including
Glass Comprising Copper and a Cellulose
[0046] The stability of a biocidal dispersion including
Guardiant.TM. and a cellulose available under the trade designation
Natrosol 250 MHR.TM., available from Ashland Specialty Chemical
Company, Covington, Ky. was studied by varying the weight
percentages of each component. Results are shown in Table 3, below.
In Table 3, "Y" indicates a stable suspension (e.g., no
sedimentation), "N" indicates an unstable suspension (e.g.,
sedimentation present), and "N/A" indicates that the mixture was
not tested.
TABLE-US-00003 TABLE 3 Stability of compositions including Natrosol
250 MHR .TM. and Guardiant .TM. Guardiant .TM. wt % Natrosol 250
MHR .TM. wt % Stable? 10 0.75 N 10 1 Y 10 1.5 Y 10 3 N 15 0.75 N 15
1 Y 15 1.5 Y 20 0.75 Y 20 1 Y 20 1.5 Y
Working Example 4: Stability of Biocidal Dispersions Including
Glass Comprising Copper and an Acrylic Acid
[0047] The stability of a biocidal dispersion including
Guardiant.TM. and an alkali soluble emulsion available under the
trade designation Acrysol ASE-60.TM., available from Dow Chemical,
Midland Hills, Mich. was studied by varying the weight percentages
of each component. A buffer was added to bring the pH to a desired
value in a range of from about 3 to about 6. Results are shown in
Table 4, below. In Table 4, "Y" indicates a stable suspension
(e.g., no sedimentation) and "N" indicates an unstable suspension
(e.g., sedimentation present.
TABLE-US-00004 TABLE 4 Stability of compositions including Natrosol
250 MHR .TM. and Acrysol ASE-60 .TM. pH Acrysol 60 wt % Guardiant
.TM. wt % Stable? 6.00 0.08 10 N 6.00 0.08 20 N 5.50 0.13 10 N 5.50
0.13 20 N 4.70 0.20 10 N 4.70 0.20 20 N 4.00 0.28 10 N 4.00 0.28 20
N 3.40 0.45 10 Y 3.40 0.45 20 Y
Working Example 5: Determining the Minimum Bactericidal
Concentration of Compositions Including Acrysol ASE-60.TM. and
Guardiant.TM.
[0048] To determine the minimum bactericidal a sample was prepared.
The sample included 20 wt % Guardiant.TM. and Acrysol ASE-60.TM..
For the sample, 10 microcentrifuge tubes were prepared along with
an additional blank tube. 500 .mu.L of a 1:500 DI water:Tryptic Soy
Broth was added to each tube (except the blank, which had 500 .mu.L
of the broth). One of the 10 microcentrifuge tubes was vortexed and
100 .mu.L of broth was removed and added to second tube. This was
repeated for the remaining microcentrifuge tubes (except for the
blank) to make serial dilutions. 50 .mu.L of Pseudomonas aeruginosa
was added to each microcentrifuge tube (including the blank). The
microcentrifuge tubes were incubated for 24 hours at 37.degree. C.
after which time 100 .mu.L of each tube's contents were removed and
plated. The plates were incubated for 24 hours at 37.degree. C.
after which time the plate were observed for colonies. The results
are shown in Table 5. In Table 5, "-" indicates no bacterial
recovery, "+" indicates trace contamination (<10 colonies), "++"
indicates light contamination (<100 colonies), and "+++"
indicates heavy contamination (continuous smear or growth).
TABLE-US-00005 TABLE 5 Minimal Bactericidal Concentration of
compositions including Natrosol plus 330 PA .TM. and Acrysol ASE-60
.TM. Tube Dilution Sample 1 1 1000000 - 2 10000 - 3 1000 +++ 4 100
+++ 5 10 +++ 6 1 +++ 7 0.1 +++ 8 0.01 +++ 9 0.001 +++ 10 0.0001 +++
11 Blank +++
[0049] The terms and expressions that have been employed are used
as terms of description and not of limitation, and there is no
intention in the use of such terms and expressions of excluding any
equivalents of the features shown and described or portions
thereof, but it is recognized that various modifications are
possible within the scope of the examples of the present
disclosure. Thus, it should be understood that although the present
disclosure has been specifically disclosed by specific examples and
optional features, modification and variation of the concepts
herein disclosed can be resorted to by those of ordinary skill in
the art, and that such modifications and variations are considered
to be within the scope of examples of the present disclosure.
Additional Examples
[0050] The following exemplary examples are provided, the numbering
of which is not to be construed as designating levels of
importance:
[0051] Example 1 provides a biocidal dispersion comprising:
[0052] one or more inorganic glass comprising copper particles;
and
[0053] a dispersant, a thickener, or a mixture thereof,
[0054] wherein the inorganic glass comprising copper is
homogenously distributed about the biocidal dispersion and is in a
range of from about 3 wt % to about 88 wt % of the biocidal
dispersion.
[0055] Example 2 provides the biocidal dispersion of Example 1,
wherein the one or more inorganic glass comprising copper particles
are in a range of from about 42 wt % to about 85 wt % of the
biocidal dispersion.
[0056] Example 3 provides the biocidal dispersion of Example 2,
wherein one or more inorganic glass comprising copper particles are
in a range of from about 10 wt % to about 22 wt % of the biocidal
dispersion.
[0057] Example 4 provides the biocidal dispersion of any one of
Examples 1-3, wherein a median size of the one or more inorganic
glass comprising copper particles are in a range of from about 1
.mu.m to about 15 .mu.m.
[0058] Example 5 provides the biocidal dispersion of any one of
Examples 1-4, wherein a median size of the one or more inorganic
glass comprising copper particles are in a range of from about 3
.mu.m to about 8 .mu.m.
[0059] Example 6 provides the biocidal dispersion of any one of
Examples 1-5, wherein the one or more inorganic glass comprising
copper particles independently comprise an inorganic glass
comprising SiO.sub.2, Al.sub.2O.sub.3, CaO, MgO, P.sub.2O.sub.5,
B.sub.2O.sub.3, K.sub.2O, ZnO, Fe.sub.2O.sub.3, or a mixture
thereof.
[0060] Example 7 provides the biocidal dispersion of any one of
Examples 1-6, wherein the one or more inorganic glass comprising
copper particles independently comprise an inorganic glass
comprising SiO.sub.2 nanoparticles, alumina nanoparticles, or
mixtures thereof.
[0061] Example 8 provides the biocidal dispersion of any one of
Examples 1-7, wherein the copper is independently in a range of
from about 25 wt % to about 40 wt % of the one or more inorganic
glass comprising copper particles.
[0062] Example 9 provides the biocidal dispersion of any one of
Examples 1-8, wherein the copper is independently Cu metal,
Cu.sup.+, Cu.sup.2+, or a combination of Cu.sup.+ and
Cu.sup.2+.
[0063] Example 10 provides the biocidal dispersion of any one of
Examples 1-9, wherein the dispersant, the thickener, or mixture
thereof, comprises an organic solution or an aqueous solution.
[0064] Example 11 provides the biocidal dispersion of any one of
Examples 1-10, wherein the dispersant, the thickener, or mixture
thereof, comprises cellulose, an acrylic acid containing polymer, a
urethane, or a mixture thereof.
[0065] Example 12 provides the biocidal dispersion of any one of
Examples 1-11, wherein the thickener comprises hydroxyethyl
cellulose, methyl cellulose, carboxymethyl cellulose, or a mixture
thereof.
[0066] Example 13 provides the biocidal dispersion of any one of
Examples 1-12, further comprising a pH modifier.
[0067] Example 14 provides the biocidal dispersion of Example 13,
wherein a pKa of the pH modifier is in a range of from about 4.7 to
about 14.
[0068] Example 15 provides the biocidal dispersion of any one of
Examples 13 or 14, wherein a pKa of the pH modifier is in a range
of from about 7 to about 9.
[0069] Example 16 provides the biocidal dispersion of any one of
Examples 13-15, wherein the pH modifier is in a range of from about
0.01 wt % to about 5 wt % of the biocidal dispersion.
[0070] Example 17 provides the biocidal dispersion of any one of
Examples 13-16, wherein the pH modifier is in a range of from about
0.1 wt % to about 1.3 wt % of the biocidal dispersion.
[0071] Example 18 provides the biocidal dispersion of any one of
Examples 13-17, wherein the pH modifier is selected from the group
consisting of Group (I) hydroxides; Group (II) hydroxides; and
organic amines.
[0072] Example 19 provides the biocidal dispersion of any one of
Examples 13-18, wherein the pH modifier is selected from metal
hydroxides, ammonium hydroxide, and amines, wherein the amines are
amines of the formula NH.sub.2R, wherein R is selected from the
group consisting of H, OR' or --R'--OH, wherein R' is selected from
the group consisting of H, alkane, and alkylene.
[0073] Example 20 provides the biocidal dispersion of any one of
Examples 13-19, wherein the pH modifier comprises potassium
hydroxide, sodium hydroxide, 2-amino-2methyl-1-propanol, ammonia,
2-dimethylamino-2-methyl-1-propanol, 2-butylaminoethanol,
N-methylethanolamine, 2-amino-2-methyl-1-propanol,
monoisopropanolamine, monoethanolamine, N,N dimethylethanolamine,
N-butyldiethanolamine, 2-amino-2-ethyl-1,3-propanediol,
2-amino-2-hydroxymethyl-1,3-propanediol, triethanolamine, or a
mixture thereof.
[0074] Example 21 provides the biocidal dispersion of any one of
Examples 13-20, wherein the pH modifier comprises a mixture of at
least one of potassium hydroxide and sodium hydroxide and at least
one of 2-amino-2methyl-1-propanol and ammonium, wherein at least
one of potassium hydroxide and sodium hydroxide, or a mixture
thereof are the major component of the pH modifier mixture.
[0075] Example 22 provides the biocidal dispersion of any one of
Examples 1-21, wherein the biocidal dispersion further comprises a
solvent.
[0076] Example 23 provides the biocidal dispersion of Example 22,
wherein the solvent is an aqueous solvent or an organic
solvent.
[0077] Example 24 provides the biocidal dispersion of Example 23,
wherein the organic solvent comprises isopropanol, xylene, butyl
acetate, or a mixture thereof.
[0078] Example 25 provides the biocidal dispersion of any one of
Examples 1-24, further comprising a surfactant.
[0079] Example 26 provides the biocidal dispersion of Example 25,
wherein the surfactant is in a range of from about 0.5 wt % to
about 40 wt % of the biocidal dispersion.
[0080] Example 27 provides the biocidal dispersion of any one of
Examples 25 or 26, wherein the surfactant is in a range of from
about 1 wt % to about 10 wt % of the biocidal dispersion.
[0081] Example 28 provides the biocidal dispersion of any one of
Examples 1-27, further comprising a defoamer or air release
agent.
[0082] Example 29 provides the biocidal dispersion of Example 28,
wherein the defoamer or air release agent is in a range of from
about 0.5 wt % to about 40 wt % of the biocidal dispersion.
[0083] Example 30 provides the biocidal dispersion of any one of
Examples 28 or 29, wherein the defoamer or air release agent is in
a range of from about 1 wt % to about 10 wt % of the biocidal
dispersion.
[0084] Example 31 provides the biocidal dispersion of any one of
Examples 1-30, further comprising a clay, silica, or a mixture
thereof.
[0085] Example 32 provides the biocidal dispersion of Example 31,
wherein the clay comprises, attapulgite, laponite, bentonite, or a
mixture thereof and the silica comprises a fumed silica.
[0086] Example 33 provides the biocidal dispersion of Example 31 or
32, wherein the clay, silica, or mixture thereof is in a range of
from about 0.5 wt % to about 40 wt % of the biocidal
dispersion.
[0087] Example 34 provides the biocidal dispersion of any one of
Examples 31-33, wherein the clay is in a range of from about 1 wt %
to about 10 wt % of the biocidal dispersion.
[0088] Example 35 provides the biocidal dispersion of any one of
Examples 1-34, further comprising a stabilizer.
[0089] Example 36 provides the biocidal dispersion of Example 35,
wherein the stabilizer comprises an organophosphate, an ammonium
phosphate, a potassium tripolyphosphate, or a mixture thereof.
[0090] Example 37 provides the biocidal dispersion of any one of
Examples 35 or 36, wherein the defoamer or air release agent is in
a range of from about 0.5 wt % to about 40 wt % of the biocidal
dispersion.
[0091] Example 38 provides the biocidal dispersion of any one of
Examples 35-37, wherein the defoamer or air release agent is in a
range of from about 1 wt % to about 10 wt % of the biocidal
dispersion.
[0092] Example 39 provides the biocidal dispersion of any one of
Examples 1-38, further comprising a rheology modifier.
[0093] Example 40 provides the biocidal dispersion of Example 39,
wherein the rheology modifier is in a range of from about 0.5 wt %
to about 40 wt % of the biocidal dispersion.
[0094] Example 41 provides the biocidal dispersion of any one of
Examples 39 or 40, wherein the rheology modifier is in a range of
from about 1 wt % to about 10 wt % of the biocidal dispersion.
[0095] Example 42 provides a coating composition comprising:
[0096] the biocidal dispersion of any one of Examples 1-41;
[0097] one or more emulsion polymers;
[0098] a second pH modifier; and
[0099] a second organic solvent or a second aqueous solvent.
[0100] Example 43 provides the coating composition of Example 42,
wherein the one or more emulsion polymers have a weight-average
molecular weight of at least 15,000 Daltons.
[0101] Example 44 provides the coating composition of any one of
Examples 42 or 43, wherein the one or more emulsion polymers have a
weight-average molecular weight of at least 1,000,000 Daltons.
[0102] Example 45 provides the coating composition of any one of
Examples 42-44, wherein the one or more emulsion polymers have a
weight-average molecular weight in a range of from about 15,000
Daltons to about 5,000,000 Daltons.
[0103] Example 46 provides the coating composition of any one of
Examples 42-45, wherein the one or more emulsion polymers have a
weight-average molecular weight in a range of from about 100,000
Daltons to about 1,000,000 Daltons.
[0104] Example 47 provides the coating composition of any one of
Examples 42-46, wherein one or more emulsion polymers include a
repeating unit derived from a polymerizable phosphorous-containing
monomer, an acetoacetoxy-functional acrylate, an
acetoacetoxy-functional methacrylate, an
acetoacetoxy-ethylmethacrylate, or a mixture thereof.
[0105] Example 48 provides the coating composition of Example 47,
wherein the polymerizable phosphorous monomer comprises the
structure according to Formula I, Formula II, or a mixture
thereof:
##STR00002##
[0106] wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5, are
independently selected from --H, --OH, and substituted or
unsubstituted (C.sub.1-C.sub.20)hydrocarbyl comprising at least one
unsaturation R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 is a
polymerizable group.
[0107] Example 49 provides the coating composition of Example 48,
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5, are
independently selected from --H, --OH, substituted or unsubstituted
(C.sub.1-C.sub.20)alkyl, substituted or unsubstituted
(C.sub.1-C.sub.20)alkenyl, substituted or unsubstituted
(C.sub.1-C.sub.20)alkynyl, substituted or unsubstituted
(C.sub.1-C.sub.20)alkoxy, substituted or unsubstituted
(C.sub.1-C.sub.20)acyl, substituted or unsubstituted
(C.sub.1-C.sub.20)cycloalkyl, substituted or unsubstituted
(C.sub.1-C.sub.20)aryl, and mixtures thereof.
[0108] Example 50 provides the coating composition of any one of
Examples 42-49, wherein the one or more inorganic glass comprising
copper particles are in a range of from about 0.5 wt % to about 25
wt % of the coating composition.
[0109] Example 51 provides the coating composition of Example 50,
wherein one or more inorganic glass comprising copper particles are
in a range of from about 1 wt % to about 5 wt % of the coating
composition.
[0110] Example 52 provides the coating composition of any one of
Examples 50 or 51, wherein the second pH modifier of the biocidal
dispersion is the same pH modifier as the coating composition of
any one of Examples 42-51.
[0111] Example 53 provides the coating composition of any one of
Examples 42-52, wherein a pKa of the second pH modifier is in a
range of from about 4.7 to about 14.
[0112] Example 54 provides the coating composition of any one of
Examples 42-53, wherein a pKa of the second pH modifier is in a
range of from about 7 to about 9.
[0113] Example 55 provides the coating composition of any one of
Examples 42-54, wherein the second pH modifier is in a range of
from about 0.1 wt % to about 5 wt % of the coating composition.
[0114] Example 56 provides the coating composition of any one of
Examples 42-55, wherein the second pH modifier is in a range of
from about 0.1 wt % to about 1.3 wt % of the coating
composition.
[0115] Example 57 provides the coating composition of any one of
Examples 42-56, wherein the second pH modifier is selected from the
group consisting of Group (I) hydroxides; Group (II) hydroxides;
and organic amines.
[0116] Example 58 provides the coating composition of any one of
Examples 42-57, wherein the second pH modifier is selected from
metal hydroxides, ammonium hydroxide, and amines, wherein the
amines are amines of the formula NH.sub.2R'', wherein R'' is
selected from the group consisting of H, OR''' or --R'''--OH,
wherein R''' is selected from the group consisting of H, alkane,
and alkylene.
[0117] Example 59 provides the coating composition of any one of
Examples 42-58, wherein the second pH modifier comprises potassium
hydroxide, sodium hydroxide, 2-amino-2methyl-1-propanol, ammonia,
2-dimethylamino-2-methyl-1-propanol, 2-butylaminoethanol,
N-methylethanolamine, 2-amino-2-methyl-1-propanol,
monoisopropanolamine, monoethanolamine, N,N dimethylethanolamine,
N-butyldiethanolamine, 2-amino-2-ethyl-1,3-propanediol,
2-amino-2-hydroxymethyl-1,3-propanediol, triethanolamine, or a
mixture thereof.
[0118] Example 60 provides the coating composition of any one of
Examples 42-59, wherein the second pH modifier comprises a mixture
of at least one of potassium hydroxide and sodium hydroxide and at
least one of 2-amino-2methyl-1-propanol and ammonium, wherein at
least one of potassium hydroxide and sodium hydroxide, or a mixture
thereof are the major component of the pH modifier mixture.
[0119] Example 61 provides the coating composition of any one of
Examples 42-60, further comprising at least one colorant.
[0120] Example 62 provides the coating composition of Example 61,
wherein the colorant is in a range of from about 0.1 wt % to about
22 wt % of the coating composition.
[0121] Example 63 provides the coating composition of any one of
Examples 61 or 62, wherein the colorant is in a range of from about
1 wt % to about 5 wt % of the coating composition.
[0122] Example 64 provides the coating composition of any one of
Examples 42-63, further comprising at least one extender.
[0123] Example 65 provides the coating composition of Example 64,
wherein the extender is in a range of from about 0.1 wt % to about
15 wt % of the coating composition.
[0124] Example 66 provides the coating composition of any one of
Examples 64 or 65, wherein the extender is in a range of from about
1 wt % to about 5 wt % of the coating composition.
[0125] Example 67 provides the coating composition of any one of
Examples 42-66, wherein the pigment or extender comprises clay,
talc, TiO.sub.2, aluminum trihydrate, nepheline syenite,
CaCO.sub.3, silica, a flattening agent, barium sulfate, zinc oxide,
or a mixture thereof.
[0126] Example 68 provides the coating composition of any one of
Examples 42-67, further comprising at least one pigment.
[0127] Example 69 provides the coating composition of Example 68,
wherein the pigment is in a range of from about 0.1 wt % to about
30 wt % of the coating composition.
[0128] Example 70 provides the coating composition of any one of
Examples 68 or 69, wherein the pigment is in a range of from about
1 wt % to about 5 wt % of the coating composition.
[0129] Example 71 provides the coating composition of any one of
Examples 68-70, wherein the pigment is TiO.sub.2.
[0130] Example 72 provides the coating composition of any one of
Examples 42-71, further comprising a second defoamer or air release
agent.
[0131] Example 73 provides the coating composition of Example 72,
wherein the second defoamer or air release agent is free of a
silicone.
[0132] Example 74 provides the coating composition of any one of
Examples 31-71, wherein the second defoamer or air release agent is
the same as the defoamer or air release agent of any one of
Examples 72 or 73.
[0133] Example 75 provides the coating composition of any one of
Examples 42-74, further comprising a second rheology modifier.
[0134] Example 76 provides the coating composition of Example 75,
wherein the second rheology modifier is in a range of from about
0.1 wt % to about 5 wt % of the coating composition.
[0135] Example 77 provides the coating composition of any one of
Examples 75 or 76, wherein the second rheology modifier is in a
range of from about 1 wt % to about 4 wt % of the coating
composition.
[0136] Example 78 provides the coating composition of any one of
Examples 75-77, wherein the second rheology modifier is a thickener
comprising hydroxyethyl cellulose, methyl cellulose, carboxymethyl
cellulose, hydroxyethylcellulose, hydrophobically modified, an
alkali swellable emulsion, a hydrophobically modified ethoxylated
urethane, hydrophobically modified analogues thereof, a natural or
synthetic gum thereof, or a mixture thereof.
[0137] Example 79 provides the coating composition of any one of
Examples 42-78, wherein a viscosity of the coating composition is
in a range of from about 70 KU to about 130 KU.
[0138] Example 80 provides the coating composition of any one of
Examples 42-79, wherein a viscosity of the coating composition is
in a range of from about 80 KU to about 115 KU.
[0139] Example 81 provides the coating composition of any one of
Examples 42-80, wherein a pH of the coating composition is in a
range of from about 6 to about 9.5.
[0140] Example 82 provides the coating composition of any one of
Examples 42-81, wherein a pH of the coating composition is in a
range of from about 7.5 to about 9.
[0141] Example 83 provides the coating composition of any one of
Examples 42-82, wherein the coating composition is a paint, an
elastomeric coating, a caulk, a sealant, a floor polish, a fabric
treatment, a secondary coat, or a primer.
[0142] Example 84 provides the coating composition of any one of
Examples 42-83, wherein the coating composition is configured to
kill a microbe chosen from Staphylococcus aureus, Enterobacter
aerogenes, Pseudomonas aeruginosa, Methicillin Resistant
Staphylococcus aureus, E. coli, and mixtures thereof.
[0143] Example 85 provides the coating composition of any one of
Examples 42-84, wherein a log reduction of the coating composition
is at least about 2.
[0144] Example 86 provides the coating composition of any one of
Examples 42-85, wherein the log reduction of the coating
composition is at least 3.
[0145] Example 87 provides the coating composition of any one of
Examples 42-86, wherein a CIEL*a*b* delta E* of the coating
composition is less than about 30.
[0146] Example 88 provides the coating composition of any one of
Examples 42-87, wherein a CIEL*a*b* delta E* of the coating
composition is less than about 6.
[0147] Example 89 provides the coating composition of any one of
Examples 42-88, wherein the coating composition is free of a
sediment of the glass comprising copper.
[0148] Example 90 provides the coating composition of any one of
Examples 42-89, wherein the coating composition is free of a
sediment of the glass comprising copper for a time period in a
range of from about 1 day to about 365 days.
[0149] Example 91 provides the coating composition of any one of
Examples 42-90, wherein the coating composition is free of a
sediment of the glass comprising copper for a time period in a
range of from about 5 days to about 90 days.
[0150] Example 92 provides a method of making the biocidal
dispersion of any one of Examples 1-91, the method comprising:
[0151] combining the one or more inorganic glass comprising copper
particles and dispersant, the thickener, or mixture thereof, to
form a dispersion precursor; and
[0152] mixing the dispersion precursor to form the biocidal
dispersion.
[0153] Example 93 provides a method of making the coating
composition of any one of Examples 42-92, the method
comprising:
[0154] combining the biocidal dispersion of any one of Examples
1-41, with the one or more emulsion polymers, the second pH
modifier, and second organic solvent or second aqueous solvent.
[0155] Example 94 provides a dried product of the coating
composition of any one of Examples 42-93.
[0156] Example 95 provides the dried product of Example 94, further
comprising a secondary coat at least partially covering the dried
product.
[0157] Example 96 provides the dried product of Example 95, wherein
the secondary coat is porous.
[0158] Example 97 provides an assembly comprising:
[0159] a substrate; and
[0160] the coating composition of any one of Examples 42-93 or the
dried product of any one of Examples 94 or 95.
[0161] Example 98 provides the assembly of Example 97, wherein the
substrate comprises wood, a plastic, a metal, a ceramic, a stone,
cement, drywall, fiberboard, paint, or a mixture thereof.
[0162] Example 99 provides a method of making the assembly of any
one of Examples 97 or 98, the method comprising:
[0163] applying the coating composition to at least a portion of
the substrate; and
[0164] drying the composition thereon.
[0165] Example 100 provides the method of Example 99, wherein the
coating composition is applied to the substrate by brush, spray
coating, roller coating, curtain coating, or a combination
thereof.
[0166] Throughout this document, values expressed in a range format
should be interpreted in a flexible manner to include not only the
numerical values explicitly recited as the limits of the range, but
also to include all the individual numerical values or sub-ranges
encompassed within that range as if each numerical value and
sub-range is explicitly recited. For example, a range of "about
0.1% to about 5%" or "about 0.1% to 5%" should be interpreted to
include not just about 0.1% to about 5%, but also the individual
values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to
0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The
statement "about X to Y" has the same meaning as "about X to about
Y," unless indicated otherwise. Likewise, the statement "about X,
Y, or about Z" has the same meaning as "about X, about Y, or about
Z," unless indicated otherwise.
[0167] In this document, the terms "a," "an," or "the" are used to
include one or more than one unless the context clearly dictates
otherwise. The term "or" is used to refer to a nonexclusive "or"
unless otherwise indicated. The statement "at least one of A and B"
has the same meaning as "A, B, or A and B." In addition, it is to
be understood that the phraseology or terminology employed herein,
and not otherwise defined, is for the purpose of description only
and not of limitation. Any use of section headings is intended to
aid reading of the document and is not to be interpreted as
limiting; information that is relevant to a section heading can
occur within or outside of that particular section.
[0168] In the methods described herein, the acts can be carried out
in any order without departing from the principles of the
disclosure, except when a temporal or operational sequence is
explicitly recited. Furthermore, specified acts can be carried out
concurrently unless explicit claim language recites that they be
carried out separately. For example, a claimed act of doing X and a
claimed act of doing Y can be conducted simultaneously within a
single operation, and the resulting process will fall within the
literal scope of the claimed process.
[0169] The term "about" as used herein can allow for a degree of
variability in a value or range, for example, within 10%, within
5%, or within 1% of a stated value or of a stated limit of a range,
and includes the exact stated value or range.
[0170] The term "substantially" as used herein refers to a majority
of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%,
96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999%
or more, or 100%.
[0171] The term "substituted" as used herein in conjunction with a
molecule or an organic group as defined herein refers to the state
in which one or more hydrogen atoms contained therein are replaced
by one or more non-hydrogen atoms. The term "functional group" or
"substituent" as used herein refers to a group that can be or is
substituted onto a molecule or onto an organic group. Examples of
substituents or functional groups include, but are not limited to,
a halogen (e.g., F, Cl, Br, and I); an oxygen atom in groups such
as hydroxy groups, alkoxy groups, aryloxy groups, aralkyloxy
groups, oxo(carbonyl) groups, carboxyl groups including carboxylic
acids, carboxylates, and carboxylate esters; a sulfur atom in
groups such as thiol groups, alkyl and aryl sulfide groups,
sulfoxide groups, sulfone groups, sulfonyl groups, and sulfonamide
groups; a nitrogen atom in groups such as amines, hydroxyamines,
nitriles, nitro groups, N-oxides, hydrazides, azides, and enamines;
and other heteroatoms in various other groups. Non-limiting
examples of substituents that can be bonded to a substituted carbon
(or other) atom include F, Cl, Br, I, OR, OC(O)N(R).sub.2, CN, NO,
NO.sub.2, ONO.sub.2, azido, CF.sub.3, OCF.sub.3, R, O (oxo), S
(thiono), C(O), S(O), methylenedioxy, ethylenedioxy, N(R).sub.2,
SR, SOR, SO.sub.2R, SO.sub.2N(R).sub.2, SO.sub.3R, C(O)R,
C(O)C(O)R, C(O)CH.sub.2C(O)R, C(S)R, C(O)OR, OC(O)R,
C(O)N(R).sub.2, OC(O)N(R).sub.2, C(S)N(R).sub.2,
(CH.sub.2).sub.0-2N(R)C(O)R, (CH.sub.2).sub.0-2N(R)N(R).sub.2,
N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R).sub.2, N(R)SO.sub.2R,
N(R)SO.sub.2N(R).sub.2, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R,
N(R)C(O)N(R).sub.2, N(R)C(S)N(R).sub.2, N(COR)COR, N(OR)R,
C(.dbd.NH)N(R).sub.2, C(O)N(OR)R, and C(.dbd.NOR)R, wherein R can
be hydrogen or a carbon-based moiety; for example, R can be
hydrogen, (C.sub.1-C.sub.100)hydrocarbyl, alkyl, acyl, cycloalkyl,
aryl, aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl; or
wherein two R groups bonded to a nitrogen atom or to adjacent
nitrogen atoms can together with the nitrogen atom or atoms form a
heterocyclyl.
[0172] The term "alkyl" as used herein refers to straight chain and
branched alkyl groups and cycloalkyl groups having from 1 to 40
carbon atoms, 1 to about 20 carbon atoms, 1 to 12 carbons or, in
some examples, from 1 to 8 carbon atoms. Examples of straight chain
alkyl groups include those with from 1 to 8 carbon atoms such as
methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and
n-octyl groups. Examples of branched alkyl groups include, but are
not limited to, isopropyl, iso-butyl, sec-butyl, t-butyl,
neopentyl, isopentyl, and 2,2-dimethylpropyl groups. As used
herein, the term "alkyl" encompasses n-alkyl, isoalkyl, and
anteisoalkyl groups as well as other branched chain forms of alkyl.
Representative substituted alkyl groups can be substituted one or
more times with any of the groups listed herein, for example,
amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen
groups.
[0173] The term "alkenyl" as used herein refers to straight and
branched chain and cyclic alkyl groups as defined herein, except
that at least one double bond exists between two carbon atoms.
Thus, alkenyl groups have from 2 to 40 carbon atoms, or 2 to about
20 carbon atoms, or 2 to 12 carbon atoms or, in some examples, from
2 to 8 carbon atoms. Examples include, but are not limited to
vinyl, --CH.dbd.CH(CH.sub.3), --CH.dbd.C(CH.sub.3).sub.2,
--C(CH.sub.3).dbd.CH.sub.2, --C(CH.sub.3).dbd.CH(CH.sub.3),
--C(CH.sub.2CH.sub.3).dbd.CH.sub.2, cyclohexenyl, cyclopentenyl,
cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl among
others.
[0174] The term "alkynyl" as used herein refers to straight and
branched chain alkyl groups, except that at least one triple bond
exists between two carbon atoms. Thus, alkynyl groups have from 2
to 40 carbon atoms, 2 to about 20 carbon atoms, or from 2 to 12
carbons or, in some examples, from 2 to 8 carbon atoms. Examples
include, but are not limited to --C.ident.CH,
--C.ident.C(CH.sub.3), --C.ident.C(CH.sub.2CH.sub.3),
--CH.sub.2C.ident.CH, --CH.sub.2C.ident.C(CH.sub.3), and
--CH.sub.2C.ident.C(CH.sub.2CH.sub.3) among others.
[0175] The term "acyl" as used herein refers to a group containing
a carbonyl moiety wherein the group is bonded via the carbonyl
carbon atom. The carbonyl carbon atom is bonded to a hydrogen
forming a "formyl" group or is bonded to another carbon atom, which
can be part of an alkyl, aryl, aralkyl cycloalkyl, cycloalkylalkyl,
heterocyclyl, heterocyclylalkyl, heteroaryl, heteroarylalkyl group
or the like. An acyl group can include 0 to about 12, 0 to about
20, or 0 to about 40 additional carbon atoms bonded to the carbonyl
group. An acyl group can include double or triple bonds within the
meaning herein. An acryloyl group is an example of an acyl group.
An acyl group can also include heteroatoms within the meaning
herein. A nicotinoyl group (pyridyl-3-carbonyl) is an example of an
acyl group within the meaning herein. Other examples include
acetyl, benzoyl, phenylacetyl, pyridylacetyl, cinnamoyl, and
acryloyl groups and the like. When the group containing the carbon
atom that is bonded to the carbonyl carbon atom contains a halogen,
the group is termed a "haloacyl" group. An example is a
trifluoroacetyl group.
[0176] The term "cycloalkyl" as used herein refers to cyclic alkyl
groups such as, but not limited to, cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In
some examples, the cycloalkyl group can have 3 to about 8-12 ring
members, whereas in other examples the number of ring carbon atoms
range from 3 to 4, 5, 6, or 7. Cycloalkyl groups further include
polycyclic cycloalkyl groups such as, but not limited to,
norbornyl, adamantyl, bornyl, camphenyl, isocamphenyl, and carenyl
groups, and fused rings such as, but not limited to, decalinyl, and
the like. Cycloalkyl groups also include rings that are substituted
with straight or branched chain alkyl groups as defined herein.
Representative substituted cycloalkyl groups can be
mono-substituted or substituted more than once, such as, but not
limited to, 2,2-, 2,3-, 2,4-2,5- or 2,6-disubstituted cyclohexyl
groups or mono-, di- or tri-substituted norbornyl or cycloheptyl
groups, which can be substituted with, for example, amino, hydroxy,
cyano, carboxy, nitro, thio, alkoxy, and halogen groups. The term
"cycloalkenyl" alone or in combination denotes a cyclic alkenyl
group.
[0177] The term "aryl" as used herein refers to cyclic aromatic
hydrocarbon groups that do not contain heteroatoms in the ring.
Thus aryl groups include, but are not limited to, phenyl, azulenyl,
heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl,
triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenylenyl,
anthracenyl, and naphthyl groups. In some examples, aryl groups
contain about 6 to about 14 carbons in the ring portions of the
groups. Aryl groups can be unsubstituted or substituted, as defined
herein. Representative substituted aryl groups can be
mono-substituted or substituted more than once, such as, but not
limited to, a phenyl group substituted at any one or more of 2-,
3-, 4-, 5-, or 6-positions of the phenyl ring, or a naphthyl group
substituted at any one or more of 2- to 8-positions thereof.
[0178] The term "alkoxy" as used herein refers to an oxygen atom
connected to an alkyl group, including a cycloalkyl group, as are
defined herein. Examples of linear alkoxy groups include but are
not limited to methoxy, ethoxy, propoxy, butoxy, pentyloxy,
hexyloxy, and the like. Examples of branched alkoxy include but are
not limited to isopropoxy, sec-butoxy, tert-butoxy, isopentyloxy,
isohexyloxy, and the like. Examples of cyclic alkoxy include but
are not limited to cyclopropyloxy, cyclobutyloxy, cyclopentyloxy,
cyclohexyloxy, and the like. An alkoxy group can include about 1 to
about 12, about 1 to about 20, or about 1 to about 40 carbon atoms
bonded to the oxygen atom, and can further include double or triple
bonds, and can also include heteroatoms. For example, an allyloxy
group or a methoxyethoxy group is also an alkoxy group within the
meaning herein, as is a methylenedioxy group in a context where two
adjacent atoms of a structure are substituted therewith.
[0179] As used herein, the term "hydrocarbyl" refers to a
functional group derived from a straight chain, branched, or cyclic
hydrocarbon, and can be alkyl, alkenyl, alkynyl, aryl, cycloalkyl,
acyl, or any combination thereof. Hydrocarbyl groups can be shown
as (C.sub.a-C.sub.b)hydrocarbyl, wherein a and b are integers and
mean having any of a to b number of carbon atoms. For example,
(C.sub.1-C.sub.4)hydrocarbyl means the hydrocarbyl group can be
methyl (C.sub.1), ethyl (C.sub.2), propyl (C.sub.3), or butyl
(C.sub.4), and (C.sub.0-C.sub.b)hydrocarbyl means in certain
examples there is no hydrocarbyl group.
[0180] The term "weight-average molecular weight" as used herein
refers to which is equal to
.SIGMA.M.sub.i.sup.2n.sub.i/.SIGMA.M.sub.in.sub.i, where n.sub.i is
the number of molecules of molecular weight M.sub.i. In various
examples, the weight-average molecular weight can be determined
using light scattering, small angle neutron scattering, X-ray
scattering, gel permeation chromatography, and sedimentation
velocity.
[0181] The polymers described herein can terminate in any suitable
way. In some examples, the polymers can terminate with an end group
that is independently chosen from a suitable polymerization
initiator, --H, --OH, a substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbyl (e.g., (C.sub.1-C.sub.10)alkyl or
(C.sub.6-C.sub.20)aryl) interrupted with 0, 1, 2, or 3 groups
independently selected from --O--, substituted or unsubstituted
--NH--, and --S--, a poly(substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbyloxy), and a poly(substituted or
unsubstituted (C.sub.1-C.sub.20)hydrocarbylamino).
* * * * *